Now, Jennifer Aniston is mixing business with pleasure by bringing new beau Justin Theroux to her interview with James Lipton for Inside the Actors Studio.

Theroux, 39, "was sitting in the front row, and she made eye contact with him," second-year Actors Studio MFA student Christina Schudel told PEOPLE at Thursday's New York taping with Aniston, 42. The interview will air next month on Bravo.

"Whenever there would be a lull, she would just look at him and give him a wink and go back to what she was doing," says Schudel.

Aniston was also clearly a hit with the crowd – which roared with laughter after Lipton asked what drew the actress to the 2006 movie The Break-Up.

Replied Aniston: "Well, you know it's something I have a lot of experience with."

"She was just so relaxed and so open," observed Schudel. "So lovable from beginning to end. Such a sweetheart."

Lipton, who chatted with the Horrible Bosses star for nearly three hours, says he was completely captivated by Aniston's warm personality.

"She's as quick and witty and charming as she is on screen," Lipton told PEOPLE immediately after the interview.